Fabrication of materials for water/oil separation is of great importance for industrial application. Herein, superhydrophobic and superolephilic fiber membrane were fabricated by combination of polydopamine (PDA) coating on the surface of electrospun polyether sulfone (PES) fiber membrane and subsequently chlorosilane modification. The as-prepared membrane exhibit that a statistic contact angle for water is greater than 150o and the oil can be quickly adsorbed, which indicated the property of superhydrophobicity and superolephilicity. Then the formed superhydrophobic and superolephilic fiber membrane was used for the continuous separation of water/oil mixture. The results presented in this work provide a simple, low-cost and efficient approach for application in the field of water/oil sepration.